Study On The Ullmann Reaction Of2-Chloro-5-nitrobenzoic Acid And2,4-Dichlorobenzoic Acid In Water

Nowadays, water has emerged as a versatile medium for organic chemistry withextraordinary attention having been paid to green chemistry. Water as a reactionmedium is not only inexpensive and innocuous, but also it can potentially improve thesectivites and reactivities, simplify the product purification, be prone to recycle thecatalyst and allow the mild reaction conditions. The application of water as the mediumin organic chemistry may be green and more profitable. The compounds ofN-Phenylanthranilic acid are common nonsteroidal anti-inflammarory drugs (NSAIDS),and they are also the important key intermediates for synthesis of biologically activeacridone and acridine. So synthesis of this kind of compounds aroused more and moreinterest of chemists. The most commonly method is Ullmann coupling reaction, and it isoften used organics solvent within long reaction time and poor yields. In this paper, theaim is to establish an environmental friendly，simple and efficient protocol for thesynthesis of the compounds of N-Phenylanthranilic acid in water. This dissertationcontains three parts.In the first part, the Cu, which was prepared by chemical reduction, catalyzed theUllmann reaction of2-chloro-5-nitrobenzoic acid in water. Several desired productswere synthesized at100℃within2-3h, and the Cu shows higher catalytic activitythan other cu-catalysts. This method to synthesize of the compounds ofN-Phenylanthranilic acid shows some advantages, such as simple purification of theproducts and the mild reaction conditions. However, it’s time consumption with lowyields, further study need to be conducted to clarify a more rapid and efficient syntheticmethod.In the second part, a simple, metal catalyst free, environmental-friendly andefficient procedure of Ullmann reaction for synthesis of N-substituted5-nitroanthranilicacid derivatives in superheated water with potassium carbonate as base was developed.Good isolated yields were achieved within2-3h at150-190℃. Additionally, thepresent method has many advantages, such as devoid of use of organic solvents or metalcatalysts and it affords good tolerates to alkyl amine and phenol.The third part combined the part one and the part two, the Cu, which waspreperated by chemical reduction, used to catalyze the Ullmann reaction of2,4-dichlorobenzoic acid to synthesis of4-chloro-2-(phenylamino)benzoic acid derivatives in in superheated water with potassium carbonate as at120-150℃. ByCompared with the methods the described in previous two parts, the present method hasbetter yields and the reaction conditions are more moderate. And it also has goodtolerates to alkyl amine and phenol.